Method of producing insoluble condensation products and product thereof.



' nets and Product Thereof; and I do hereby sidin FRITZ POLLAK, 0FIBZElIRJLIIiI', GERMANY.

. METHOD or rnonucinc INSOLUBLE connnnsn'rroivrnonuc'rs .AND raonuorPatented Feb. 20, 1917.

4 THEREOF. 1,216,728. Specification of Letters Patent.

No Drawing.

To all whom it may concern Be it known that I, FRrrz Format, 2. citizenof the Empire of-Austria-Hungary, iceat Berlin, in the KingdomofPrussia, erman Empire, have invented certain new and useful Improvementsin the Method of Producing Insoluble Condensation Proddeclare thefollowing to be a full, clear, and

exact description of the invention, such. as'

will enable others skilled in the art to which it appertains to make anduse the same.

Kleeber (Liebgs 'Am/n. Ghana, 263 pag. 283) has found, that if a largequantity of mineral acids reacts on a mixture of phenol and formaldehydea pink' colored resinous substance is formed. This roduct, althoughinsoluble in the usual so vents, cannot be used for technical purposeson account vof its sponginess and lack 'of homogeneity. Nor couldKleebergs process bepractised on a large scale, as it is of an explosivecharacter.

The present invention relates to the production of insoluble products bythe catalytic action of acids, but in a proper technical condition. Ihave discovered, that the quantity of acids, which Kleeberg-accordin'gto his description of the process-must have used, will have to beconsiderably diminished, when it is desired to form compact andhomogeneous masses on a large scale, suitable for technical purposes.

Furthermore I have found thatthe pink color of Kleebergs products is nota necessary property of these products, but is solely due to thepresence of a too great excess of acid and that when the quantity ofacid employed does not exceed 12% of the end product, perfectly white orslightly brownish or yellowish colored opaque masses will be formed,which are very similar to ivory in their appearance and qualities. Thequantity of acid used, therefore, determines the color of the product.They may be cut, stamped, bored, filed .or polished and are on accountof their toughness and hardness of great technical value.

I have also discovered that these insoluble products are not thecondensation products insoluble condensation-products. By means whichare first obtained, but that in a first salts.

Application filed September 14,1910. see No. 581,988. r

q of my invention it is possible to isolate these intermediary products,to shape them, to

compound them with other substances and.

finallyto transform them into the insoluble mass desired. "This presentinvention relates. also to theproduction of articles conslsting of thelatter or containing the same.

Insoluble condensation-products of phenols and formaldehyde havehitherto been formed by the condensing action of bases or The productsobtained in this manner are not identical with the products, forming theobject of the present invention,

as they are transparent and of a deep yellow,

brown or red color.

The manner of working the new process may be considerably variedaccording to the properties of the acids employed or to their quantityor to the results sought, the essential point being to regulate thequantity of acid, so as to secure the products of the kind beforementioned.

" As is well known, the power and rapidity with which dissolvedsubstances interact is often dependent upon the relative concentrationsof thedissolved substances. As can be seen from the examples, thepercentage of acid useddoesnot cause the reaction between the dissolvedcrystallized Phenol and the ordinary 40% solution of formaldehyde below100 C. i I

Example l.+18.8 parts of crystallized phenol, 8.73 parts ofparaformaldehyde and 0.04:.parts of para phenolsulfonic acid (dissolvedin water) are warmed up on a waterbath, until the paraformaldehyde hasdissolved. When this pointzis reached and the reaction takes place thetemperature of the liquid rises slightly over 100 C. At the same timethe mass boils up and gains a resinous appearance. It may now be pouredinto suitable molds, in-which it becomes hard and insoluble. at about100 C. It forms shows apink'color, but is white inside.

-Emample lI.-100 parts of crystallized phenol, 125 arts of formaldehyde40% and 0.30 parts 0 hydrochloric acid (1.19 specific weight) may bemixed and evaporated in a suitable vessel with stirrer onla waterbath,the temperature ofwhich, as is well known, is below 100 C. When about 60parts have evaporated, a reaction sets in and the temperature of theliquid rises somewhat over Bin- M,

100 Cg, Someg'timefafter, a white precipitate separated from the clearsolution. To'tliisYI add while stirring about 30 parts of 'ivaterand"evaporate this again at about 75 C." Themass is now ready to be filledinto molds,- which I heat. up to 7080 C.

until the product becomes elastic, when warm. When then the temperatureis gradually increased from 80 to 125 C. a perfectl hard and homogeneousmass will be forme When drawn it shows accurately the dimensions of themold employed. It is slightly reddish on its surface, but white inside.

' Ewample HI.A mixture of 100 parts of crystallized phenol, 250 parts offormaldehyde (45%) and 0.3-0.8 parts of hydrochloric acid (1.19 specificweight) are evaporated on a waterbath and worked up in a' similar way tothe one described in the examples I and II. The mass, which Iobtain,-although containing traces of free formaldehydeis1 without anysmell when worked up. I It is compact, white, insoluble, hard and-tough,thus forming an excellent substitute for ivory.

When the oxidation of the surface of these products is objectionable,one may carry out the process in an atmosphere of inert gas, forinstance nitrogen, hydrogen, carbonic acid or the like. Sometimes it maybe advisable to use for the same purpose a closed vessel with or'without pressure.

The mode of application or compounding of the condensation productdepends upon the results desired. As mentioned above I may interrupt theprocess at any stage and the product will remain unchanged for a longtime, when cooled down. It may then (either as a liquid or in a resinousstate orwhen the process has further progressed-as a powder) be mixedwith other substances such as asbestos, graphite, sand, powdered metals,tar, resins, oils, colors, pigments, cellulose, acetylcellulose or thelike. The mix ture may be pressed into molds hot or cold and hardened upafterward at temperatures over 100 C.

I The word phenol mentioned in this description designates not only. thefirst representative of thephenolic series but also its homologues. Imay for instance use the so called crude carbolic acid 95/100, which isa mixture of cresols and contains from 95% to 100% of cresols. In thiscase I remove the small quantity of basic substances contained in it anduse the purified product in the way described in the examples. Theinsoluble products formed therewith are very similar to those obtainedout of pure phenol. They form compact, white or slightly yellowishcolored masses and may be cut, stamped, bored or polished when hard orworked up in an intermediate liquid or viscous state.

The amount of formaldehyde to be used is not limited to the quantitiesgiven above, butmay be varied, if desired, but more than c uimolecularquantities should be prefera 1y used; When evaporated it may beregenerated by the well known suitable means.

I claim- 1. The process herein described of roducing compact, opaque,insoluble, infusible, white to yellowish colored condensation products.of phenols and formaldehyde, which consists in reacting on a body ofthe phenolic series with more than an equimolecular quantity of theformaldehyde in the presence of so small a quantity of acid thatwhitish, intermediate products are first formed, and then renderingthese white, intermediate products insoluble.

2. A method of producing homogeneous white to yellowish opaque insolubleand ivory-like products from phenol and formaldehyde in the presence ofan acid, which consists in causing concentrated formaldehyde to reactupon a dissolved phenol in the presence of'saidv acid, the quantity ofsaid acid being insufficient to start said reaction when saidformaldehyde is diluted to form a 40% solution, said substancesbeingmaintained at a temperature below 100 C. until said reaction hastaken place, whereby a fusible and soluble intermediate product isformed, and then changing said soluble and fusible intermediate productto an insoluble and infusible product, as described.

3.. A method of producing homogeneous white to yellowish opaqueinsoluble and ivory-like products from phenol and formaldehyde in thepresence of an acid, which consists in making a solution havinga'temperature below 100 (3., said solution consisting of a mixture ofphenol and'of 40% formaldehyde and said acid, the quantity of said acidbeing insuflicient to start the reaction between the phenol and theformaldehyde, concentrating said solution at a tem perature below 100 C.until reaction sets in, whereby a soluble and fusible intermediateproduct is obtained, and then converting said soluble and fusibleintermediate prodnot into an infusible and insoluble-product.

4. In the art of producing homogeneous white to yellowish opaqueinsoluble and ivory-like products from phenol and formaldehyde in thepresence of an acid, that step in t e art which consists in causing theformaldehyde and phenol to react at a temperature below 100 C. in thepresence of an acid, the quantity of said acid being so small that awhite soluble, fusible product is formed.

5. The process herein described of producing articles of compact,insoluble condensation products of phenols and formaldehyde, whichconsists in reacting on a body of the phenolic series with more than anequimolecular quantity of formaldehyde in the presence of so small aquantity of acid so that soluble, white, intermediate products are'first formed, isolating said soluble, white, intermediate products,forming articles with the said products, and rendering them insoluble bythe influence of heat.

6. As a new manufacture, a compact, insoluble, infusible, white toyellowish colored 10 opaque condensation product of phenols andforgialdehyde containing a small amount of am s. v

In testimony, that I claim the foregoing as my invention, I have signedmy name in presence of two subscribing witnesses.

FRITZ POLLAK. Witnesses:

HENRY HASPER, WOLDEMAR HAUPT.

